Method and device for etching silicon oxide

ABSTRACT

The method of dry-etching silicon oxide of the present disclosure includes reacting silicon oxide with any one of the following (A) to (C): (A) a gaseous hydrogen fluoride and a gaseous organic amine compound, (B) a gaseous hydrogen fluoride salt of an organic amine compound, and (C) a gaseous hydrogen fluoride, a gaseous organic amine compound, and a gaseous hydrogen fluoride salt of an organic amine compound in a non-plasma state.

TECHNICAL FIELD

The present disclosure relates to a method of dry-etching silicon oxidein a non-plasma state, and an etching apparatus used in the method.

BACKGROUND ART

Production of semiconductor devices includes etching of a silicon oxidefilm, such as a CVD oxide film, a thermal oxide film, or a natural oxidefilm, on a surface of a semiconductor wafer. The silicon oxide film isetched by wet etching with chemical liquids or plasma etching withreactive gas plasma.

In wet etching, chemical liquids often adversely affect parts other thanetching targets. In plasma etching, wafers are liable to electric damagederived from plasma.

To overcome the issues, dry-etching without plasma has been tried. Sometechniques of dry-etching SiO₂ without plasma are disclosed. Forexample, a hydrogen fluoride gas is used in combination with: watervapor in Patent Literature 1; gaseous methanol in Patent Literature 2;gaseous acetic acid in Patent Literature 3; and gaseous isopropylalcohol in Patent Literature 4.

For fast SiO₂ etching, techniques using a gas mixture including ahydrogen fluoride gas and an ammonia gas are studied. For example,Patent Literature 5 discloses a two-step etching involving an AFS layerforming step (chemical oxide removal; COR treatment) and a heating step(post heat treatment; PHT treatment). In the AFS layer forming step, agas mixture including HF gas and NH₃ gas is supplied to a surface of asilicon oxide film on a substrate so that the silicon oxide filmchemically reacts with the gas mixture into ammonium fluorosilicate(AFS), thereby forming an AFS layer as a reaction product on a siliconlayer of the substrate. In the heating step, the AFS layer is heated tobe sublimated or thermally decomposed without supplying the gas mixture.

CITATION LIST Patent Literature

Patent Literature 1: JP H6-181188 A

Patent Literature 2: JP H8-81788 A

Patent Literature 3: JP H9-509531 T

Patent Literature 4: JP 2001-503571 T

Patent Literature 5: JP 2007-180418 A (JP 4890025 B)

TECHNICAL PROBLEM Summary of Invention

Unfortunately, the SiO₂ etching speed is insufficient in the methods ofPatent Literatures 1 to 4.

The method of Patent Literature 5 is also unsatisfactory because, if theCOR treatment alone is performed, the AFS layer remains as a residue onthe surface of the silicon oxide film. Additionally, in order tocompletely remove a thick AFS layer formed in the COR treatment by thePHT treatment, the layer needs to be heated at higher than 200° C. Heatdamage of parts other than the silicon oxide film is concerned.

Furthermore, since the PHT treatment is conducted at a highertemperature than the COR treatment, a chamber needs to be heated orcooled every time the steps are switched, or the chamber may be replacedin each step, reducing productivity.

The present disclosure aims to provide a method of etching silicon oxidewithout plasma at a sufficient speed while generating no residue even ata low temperature of 200° C. or lower.

Solution to Problem

As a result of intensive studies, the present inventors found thatsilicon oxide reacts with HF and an organic amine compound as a baseinstead of NH₃, and that the reaction product sublimates at a much lowertemperature than ammonium fluorosilicate and can be removed at a lowtemperature. Accordingly, the present disclosure was completed.

Specifically, the dry-etching method of the present disclosure includesreacting silicon oxide with any one of the following (A) to (C): (A) agaseous hydrogen fluoride and a gaseous organic amine compound, (B) agaseous hydrogen fluoride salt of an organic amine compound, and (C) agaseous hydrogen fluoride, a gaseous organic amine compound, and agaseous hydrogen fluoride salt of an organic amine compound in anon-plasma state.

Herein, etching in a plasma state refers to etching involving generatinglow-temperature gas plasma in a reactor by introducing a halogen gas orthe like at a pressure of about 0.1 to 10 Torr into the reactor andapplying a high-frequency power to an outer coil or a counter electrode,and etching silicon oxide or the like with a halogen-based activechemical generated in the reactor.

The etching method of the present disclosure involves reacting theabove-mentioned gas in a non-plasma state, thereby dry-etching siliconoxide without generating the above-mentioned gas plasma.

The etching apparatus of the present disclosure includes: a treatmentcontainer provided with a stage configured to carry a substrateincluding a silicon oxide film; a hydrogen fluoride gas supplierconfigured to supply a treatment gas including a hydrogen fluoride intothe treatment container; an organic amine compound gas supplierconfigured to supply a treatment gas including an organic amine compoundinto the treatment container; a vacuum evacuator configured to reducethe pressure inside the treatment container; and a heater configured toheat the stage.

Advantageous Effects of Invention

The dry-etching method of the present disclosure enables etching ofsilicon oxide in a non-plasma state at a sufficient speed whilegenerating no residue even at a low temperature of 200° C. or lower.

The etching apparatus of the present disclosure having theabove-mentioned structure can etch silicon oxide in a non-plasma statewhile generating no residue by: introducing a hydrogen fluoride gas andan organic amine compound via the hydrogen fluoride gas supplier and theorganic amine compound gas supplier, respectively, into the treatmentcontainer provided with a substrate including silicon oxide; controllingthe pressure with the vacuum evacuator; and heating the substrate withthe heater.

BRIEF DESCRIPTION OF DRAWINGS

FIG. 1 is a schematic diagram of the etching apparatus of the presentdisclosure used in examples and comparative examples.

DESCRIPTION OF EMBODIMENTS

The present disclosure is specifically described in detail below. Theessential features described below are examples of embodiments of thepresent disclosure and are not limited to the specific descriptions. Thepresent disclosure may be variously modified and enabled within thescope of the gist thereof.

The dry-etching method of the present disclosure includes reactingsilicon oxide with any one of the following (A) to (C): (A) a gaseoushydrogen fluoride and a gaseous organic amine compound, (B) a gaseoushydrogen fluoride salt of an organic amine compound, and (C) a gaseoushydrogen fluoride, a gaseous organic amine compound, and a gaseoushydrogen fluoride salt of an organic amine compound in a non-plasmastate.

Specific embodiments of the dry-etching method of the present disclosuremay be classified into two embodiments. A first embodiment of theetching is conducted by supplying a treatment gas including a hydrogenfluoride and an organic amine compound to the etching apparatus. Asecond embodiment of the etching is conducted by separately supplying atreatment gas including an organic amine compound and a treatment gasincluding a hydrogen fluoride to the etching apparatus.

First Embodiment

In the first embodiment, a treatment gas (dry-etching gas) including ahydrogen fluoride and an organic amine compound is supplied to theetching apparatus so that the treatment gas makes contact with siliconoxide, thereby etching the silicon oxide.

When silicon oxide is made in contact with a treatment gas including ahydrogen fluoride and an organic amine compound, the silicon oxidechemically reacts with the hydrogen fluoride and the organic aminecompound to be converted into a reaction product such as an organicamine salt of hexafluorosilicic acid. Immediately upon generation, thereaction product sublimates into a gas or is thermally decomposed into agas. Thus, the silicon oxide is removed. Herein, the term “sublimation”may refer to conversion of a solid into a gas without thermaldecomposition and conversion of a solid into a component of a gasthrough thermal decomposition.

The hydrogen fluoride gas and the organic amine compound gas may beseparately supplied and mixed to form a treatment gas in the etchingapparatus. Alternatively, the hydrogen fluoride and the organic aminecompound may be preliminarily reacted with each other into a hydrogenfluoride salt of the organic amine, and then the salt may be supplied asa dry-etching gas into the etching apparatus. In the case of separatelysupplying the hydrogen fluoride gas and the organic amine compound gasand mixing them in the etching apparatus, a hydrogen fluoride salt of atleast a portion of the organic amine is generated in the etchingapparatus. In the etching apparatus, the three components, i.e., thegaseous hydrogen fluoride, the gaseous organic amine compound, and thegaseous hydrogen fluoride salt of the organic amine compound may makecontact with the silicon oxide. Alternatively, only the gaseous hydrogenfluoride salt of the organic amine compound may make contact with thesilicon oxide, or only the gaseous hydrogen fluoride and the gaseousorganic amine compound may make contact with the silicon oxide.

In any option, an organic amine salt of hexafluorosilicic acid isgenerated as a result of the reaction with the silicon oxide.

The ratio of the organic amine compound to the hydrogen fluorideincluded in the treatment gas, as determined by dividing the number ofmoles of the organic amine compound by the number of moles of thehydrogen fluoride, is preferably 0.001 or higher but 100 or lower, morepreferably 0.01 or higher but 10 or lower, particularly preferably 0.1or higher but 5 or lower.

Examples of the organic amine compound include a compound represented bythe following formula (1):

wherein N represents a nitrogen atom, R¹ represents a C1-C10 hydrocarbongroup optionally having a ring, a heteroatom, or a halogen atom, and R²and R³ each represent a hydrogen atom or a C1-C10 hydrocarbon groupoptionally having a ring, a heteroatom, or a halogen atom, providedthat: the hydrocarbon group, when it has a carbon number of three ormore, may have a branched chain structure or a ring structure; theheteroatom in the hydrocarbon group is a nitrogen atom, an oxygen atom,a sulfur atom, or a phosphorus atom; R¹ and R₂, when both of them arehydrocarbon groups having a carbon number of one or more, may bedirectly bonded to each other to form a ring structure; R¹ and R², whenthey are directly bonded to each other via a double bond to form a ringstructure, they may form an aromatic ring in the absence of R³; and R¹,R², and R³ may be hydrocarbon groups which are the same as or differentfrom one another.

Examples of R¹ include a methyl group, an ethyl group, a propyl group,and a butyl group. Hydrogen atoms in the organic groups may be partiallyreplaced by a halogen atom such as fluorine or chlorine. Examples ofeach of R² and R³ include a hydrogen atom, a methyl group, an ethylgroup, a propyl group, and a butyl group. Hydrogen atoms in the organicgroups may be all or partially replaced by a halogen atom such asfluorine or chlorine. The organic amine compound represented by theformula (1) may be a heterocyclic amine having a five-membered ringstructure or a six-membered ring structure.

Specific examples of the organic amine compound include monomethylamine,dimethylamine, trimethylamine, dimethylethylamine, diethylmethylamine,monoethylamine, diethylamine, triethylamine, mono-normal propylamine,di-normal propylamine, monoisopropylamine, diisopropylamine,monobutylamine, dibutylamine, mono-tertiary butylamine, di-tertiarybutylamine, pyrrolidine, piperidine, piperazine, pyridine, and pyrazine.Specific examples also include the foregoing compounds in which all orpart of C-H bonds are replaced by C-F bonds, such astrifluoromethylamine, 1,1,1-trifluorodimethylamine,perfluorodimethylamine, 2,2,2-trifluoroethylamine, perfluoroethylamine,bis(2,2,2-trifluoroethyl)amine, perfluorodiethylamine, and3-fluoropyridine. These organic amine compounds are preferred becausethey each have a conjugated acid having a pKa of not lower than 3.2,which is the pKa of HF, and thus can form a salt with a hydrogenfluoride, have a constant vapor pressure in a temperature range from 20°C. to 100° C., and can be supplied as gas without decomposition in thetemperature range.

In terms of easy availability, the organic amine compound is preferablymonomethylamine, dimethylamine, trimethylamine, monoethylamine,monopropylamine, isopropylamine, 1,1,1-trifluorodimethylamine,2,2,2-trifluoroethylamine, or bis(2,2,2-trifluoroethyl)amine.

To etch the silicon oxide faster, the organic amine compound ispreferably a secondary amine or a tertiary amine. Specific examples ofthe secondary amine include dimethylamine, diethylamine, di-normalpropylamine, diisopropylamine, dibutylamine, and di-tertiary butylamine.Specific examples of the tertiary amine include trimethylamine,dimethylethylamine, diethylmethylamine, and triethylamine.

The treatment gas may substantially consist only of the hydrogenfluoride and the organic amine compound. The treatment gas mayoptionally include an inert gas. Examples of the inert gas include noblegas such as argon gas, and nitrogen gas. The proportion of the inert gasin the treatment gas, as determined by dividing the number of moles ofthe inert gas by the number of moles of the hydrogen fluoride, ispreferably 0 or higher but 100 or lower, more preferably 10 or lower,particularly preferably 5 or lower.

The treatment gas makes contact with the silicon oxide at not lower thana temperature at which a reaction product of the silicon oxide, thehydrogen fluoride, and the organic amine compound is sublimated orthermally decomposed. Taking productivity or damage of a substrate to betreated into consideration, the contact temperature is preferably 200°C. or lower, more preferably 150° C. or lower, particularly preferably120° C. or lower. The contact temperature is preferably 20° C. orhigher, more preferably 50° C. or higher, particularly preferably 80° C.or higher.

The treatment gas makes contact with the silicon oxide at any pressure.Yet, the pressure is preferably 0.1 Pa or higher but 100 kPa or lower,more preferably 0.5 Pa or higher but 50 kPa or lower, particularlypreferably 1 Pa or higher but 10 kPa or lower.

The temperature and pressure during the contact between the treatmentgas and the silicon oxide are each not necessarily constant and may bechanged at certain intervals. For example, the temperature may beincreased or the pressure may be reduced in a time period to facilitatethe sublimation of the reaction product.

This embodiment may include a COR step of contacting the treatment gaswith the silicon oxide and a PHT step of sublimating a reaction productwithout supplying the treatment gas as disclosed in Patent Literature 5.In such an embodiment, the PHT step may be conducted at 200° C. orlower.

The silicon oxide may be a silicon oxide film on a semiconductorsubstrate. The semiconductor substrate is usually a silicon substrate. Afilm other than a silicon oxide film, such as a silicon film, a siliconnitride film, or a metal film, may be exposed to the surface of thesemiconductor substrate.

For a substrate to be treated where both a silicon oxide film and asilicon nitride film are exposed, the etching method of this embodimentenables selective etching of the silicon oxide film relative to thesilicon nitride film. The silicon oxide/silicon nitride etchingselection ratio is preferably 2.5 or higher, more preferably 5 orhigher, still more preferably 8 or higher, particularly preferably 10 orhigher. Herein, the term “silicon oxide/silicon nitride etchingselection ratio” refers to a quotient of a division of the etching speedof the silicon oxide film by the etching speed of the silicon nitridefilm. Herein, the term “etching speed” refers to a quotient of adivision of a change in the thickness of the film between before andafter the etching by the duration of the etching. Thus, a higher siliconoxide/silicon nitride etching selection ratio means that the siliconoxide is etched at a higher rate than the silicon nitride.

The dry-etching method of the present disclosure can be used toselectively dry-etch SiO₂ in a structure in where SiO₂ is adjacent toSiN in production of a semiconductor device on a semiconductorsubstrate. Examples of the structure include a structure in which a SiNfilm covers a SiO₂ film and a structure in which a SiO₂ film and a SiNfilm are sequentially stacked. In an exemplary process of producing athree-dimensional memory, a SiO₂/SiN multilayer film is formed on asemiconductor substrate, a through hole is formed in the multilayerfilm, and an etching gas is supplied via the through hole to selectivelyetch the SiO₂ while allowing the SiN to remain by the dry-etching methodof the present disclosure. Thus, a semiconductor device including alarge number of parallel SiN layers with spaces therebetween can beproduced.

The method of producing a semiconductor device of the present disclosuremay be applied to not only production of the above-describedsemiconductor device but also production of a semiconductor deviceinvolving etching of a silicon oxide film formed on a substrate.

Second Embodiment

The etching in the second embodiment of the dry-etching method of thepresent disclosure is conducted by separately supplying a treatment gasincluding an organic amine compound and a treatment gas including ahydrogen fluoride into an etching apparatus. Specifically, in the secondembodiment, a treatment gas including an organic amine compound issupplied to silicon oxide in an etching apparatus, followed by optionalevacuation, and then a treatment gas including a hydrogen fluoride issupplied to the etching apparatus.

Examples of the organic amine compound include the compounds representedby the formula (1) for the first embodiment.

Presumably, when an organic amine is firstly introduced into an etchingapparatus so that silicon oxide makes contact with the gaseous organicamine compound, the organic amine compound is adsorbed to the surface ofthe silicon oxide. The subsequent introduction of a gaseous hydrogenfluoride into the etching apparatus allows the hydrogen fluoride to makecontact with the silicon oxide with the organic amine compound adsorbedthereto. Thus, the adsorbed organic amine compound is presumablyconverted into a reaction product such as an organic amine salt ofhexafluorosilicic acid. The final reaction product is an organic aminesalt of hexafluorosilicic acid that is of the same kind of the reactionproduct in the first embodiment. The compound is sublimated into a gasimmediately upon generation or thermally decomposed into a gas.

The gas to be introduced into the etching apparatus may substantiallyconsist only of the organic amine or substantially only of the hydrogenfluoride. The organic amine and the hydrogen fluoride each mayoptionally include an inert gas. Examples of the inert gas include noblegas such as argon gas, and nitrogen gas. The proportion of the inert gasin the treatment gas, as determined by dividing the number of moles ofthe inert gas by the number of moles of the hydrogen fluoride or thenumber of moles of the organic amine, is preferably 0 or higher but 100or lower, more preferably 10 or lower, particularly preferably 5 orlower.

In supplying each treatment gas to the silicon oxide, the organic aminecompound is made in contact with the silicon oxide at preferably 200° C.or lower, more preferably 150° C. or lower, particularly preferably 120°C. or lower. The hydrogen fluoride is made in contact with the siliconoxide at preferably 200° C. or lower, more preferably 150° C. or lower,particularly preferably 120° C. or lower. Each compound is made incontact with the silicon oxide at, for example, preferably 20° C. orhigher, more preferably 50° C. or higher, particularly preferably 80° C.or higher. The contact temperature for the organic amine compound andthe silicon oxide may be the same as or different from that for thehydrogen fluoride and the silicon oxide.

The organic amine compound or the hydrogen fluoride is made in contactwith the silicon oxide at preferably 0.1 Pa or higher but 100 kPa orlower, more preferably 0.5 Pa or higher but 50 kPa or lower,particularly preferably 1 Pa or higher but 10 kPa or lower.

The structure of the silicon oxide as an etching target is preferablythe same as the structure in the first embodiment. The etching method ofthe second embodiment enables selective etching of the silicon oxidefilm relative to the silicon nitride film. The silicon oxide/siliconnitride etching selection ratio is preferably 2.5 or higher, morepreferably 5 or higher, particularly preferably 10 or higher.

The supply of the treatment gas including the organic amine compound maybe conducted after the supply of the treatment gas including thehydrogen fluoride gas. The treatment gas including the hydrogen fluoridegas and the treatment gas including the organic amine compound maysequentially be alternately supplied.

Etching Apparatus

The etching methods of the embodiments are conducted using an etchingapparatus including: a treatment container provided with a stageconfigured to carry a substrate to be treated including a silicon oxidefilm; a hydrogen fluoride gas supplier configured to supply a treatmentgas including a hydrogen fluoride into the treatment container; anorganic amine compound gas supplier configured to supply a treatment gascontaining an organic amine compound into the treatment container; avacuum evacuator configured to reduce the pressure inside the treatmentcontainer; and a heater configured to heat the stage. The etchingapparatus may further include an inert gas supplier configured to supplyan inert gas into the treatment container, if necessary.

FIG. 1 is a schematic diagram of a reactor 1 that is one example of theetching apparatus according to an embodiment of the present disclosure.

The reactor 1 includes a chamber (treatment container) 2 in which astage 3 to be heated by a heater 8 is provided. Other heaters (notshown) are provided around the chamber 2 to heat a chamber wall. Atreatment gas is introduced through a hydrogen fluoride gas supplier 5 aand an organic amine compound gas supplier 5 b which are provided on theupper part of the chamber so that the treatment gas makes contact with asample (substrate to be treated) 4 carried on the stage 3. The gas inthe chamber 2 is emitted through a gas emission line 6. The chamber 2includes an inert gas supplier 5 c through which an inert gas isoptionally supplied. The gas emission line is connected to a vacuum pump(vacuum evacuator, not shown) configured to reduce the pressure in thechamber 2. The chamber 2 includes a manometer 7. An organic aminehydrogen fluoride salt gas supplier may be provided instead of thehydrogen fluoride gas supplier 5 a and the organic amine compound gassupplier 5 b.

The operation to remove silicon oxide in a sample 4 (substrate includinga silicon oxide film) in the embodiments is briefly described below.

The stage 3 is heated to a predetermined temperature by the heater 8.Then, a treatment gas is introduced into the chamber 2 through thehydrogen fluoride gas supplier 5 a and the organic amine compound gassupplier 5 b under the conditions according to the first embodiment orthe second embodiment so that the sample 4 makes contact with thetreatment gas. A reaction product generated by the reaction issublimated immediately upon generation and emitted from the chamber 2through the gas emission line 6.

The reactor 1 further includes a regulator. The regulator may be acomputer, for example, including a program, a memory, and a CPU. Theprogram includes steps to work a series of operations in the firstembodiment or the second embodiment. According to the program, thetemperature of the sample 4, open-close of a valve in each gas supplier,the flow rate of each gas, and the pressure inside the chamber 2 arecontrolled. The program is saved in a computer storage medium such as acompact disc, a hard disc, a magneto-optical disc, or a memory card andis installed in the regulator.

Effects of Embodiments

The first embodiment of the dry-etching method or the second embodimentof the dry-etching method enables etching of silicon oxide withoutplasma even at a low temperature of 200° C. or lower.

In the first embodiment of the dry-etching method or the secondembodiment of the dry-etching method, the etching can be conductedwithout leaving a residue of the formation of a reaction product layeron the surface of the silicon oxide even at a low temperature of 200° C.or lower.

Thus, the silicon oxide can be etched in one step without a PHTtreatment to sublimate the reaction product. Hence, the silicon oxidecan be more efficiently etched than in a cycle etching in which a CORtreatment and a PHT treatment are alternately conducted.

In the first embodiment of the dry-etching method or the secondembodiment of the dry-etching method, the silicon oxide can be etched bythe method of the present disclosure even without heating a substrate toa high temperature of higher than 200° C. Such a method can be appliedto substrates including materials with low heat resistance.

The first embodiment of the dry-etching method or the second embodimentof the dry-etching method enables selective etching of the silicon oxiderelative to polycrystalline silicon. In the etching methods of theembodiments, an organic amine compound is used so that silicon oxide canbe etched at a higher silicon oxide/silicon nitride etching selectionratio than in conventional methods using ammonia. In the etching methodsof the embodiments, the silicon oxide can be etched faster than inmethods using water or alcohol.

EXAMPLES

Examples of the present disclosure and comparative examples arepresented below, but the present disclosure is not limited to theexamples.

A reactor illustrated in FIG. 1 was used in the examples and comparativeexamples. As the sample 4, a silicon wafer A including a polycrystallinesilicon film, a silicon wafer B including a thermal oxide film, or asilicon wafer C including a silicon nitride film was used.

Examples 1-1 to 1-11, Comparative Examples 1-1 to 1-8

The wafer A, B, or C was placed on a stage in the chamber. The chamberwas evacuated, and the temperature of the stage was adjusted to apredetermined temperature indicated in Table 1-1 below. Then, atreatment gas was supplied into the chamber, and the state wasmaintained for 30 seconds. Subsequently, the atmosphere in the chamberwas evacuated to 10 Pa or lower and then replaced with an inert gas.Next, the wafer A, B, or C was taken out, and its thickness wasmeasured, thereby evaluating the etching amount. Separately, a surfaceof the thermal oxide film on the silicon wafer B after the etching wasobserved with an optical microscope to examine the presence of residueson the surface.

Table 1-1 shows the types and flow rates of organic amines, flow rate ofHF, pressure, temperature, and duration of etching, and Table 1-2 showsevaluation results after etching.

In Example 1-1, HF gas and trimethylamine gas were simultaneouslyintroduced from different inlets into the chamber, and a gas mixture ofthe gases prepared in the chamber was made in contact with the sample.In Example 1-2, a gas prepared by gasifying trimethylamine hydrofluoride(NMe₃·HF) was supplied as the treatment gas into the chamber. InExamples 1-3, 1-4, and 1-8 and Comparative Example 1-1, dimethylamine,diethylamine, monomethylamine, and ammonia, respectively, were usedinstead of the trimethylamine in Example 1-1. In Comparative Example1-2, ammonium fluoride (NH₄F) was used instead of the trimethylaminehydrofluoride in Example 1-2. Examples 1-5 to 1-7 and 1-9 andComparative Example 1-3 were conducted at different temperatures. InExamples 1-10 and 1-11, the flow rates of the trimethylamine and the HFgas were changed from the flow rates in Example 1-1. In ComparativeExamples 1-4 and 1-5, only HF diluted with argon gas and onlytrimethylamine diluted with argon gas, respectively, were supplied. InComparative Examples 1-6, 1-7, and 1-8, gases prepared by gasifyingwater, methanol, and isopropyl alcohol, respectively, were suppliedinstead of the trimethylamine in Example 1-1.

TABLE 1-1 Etching conditions Organic amine, etc. HF Ar Flow flow flowTemper- rate rate rate Pressure ature Duration Type [sccm] [sccm] [sccm][Torr] [° C.] [sec] Example 1-1 Trimethylamine 50 50 0 30 100 30 Example1-2 Trimethylamine 50 0 50 10 100 30 hydrofluoride Example 1-3Dimethylamine 50 50 0 30 100 30 Example 1-4 Diethylamine 50 50 0 30 10030 Example 1-5 Trimethylamine 50 50 0 30 60 30 Example 1-6 Dimethylamine50 50 0 30 60 30 Example 1-7 Diethylamine 50 50 0 30 60 30 Example 1-8Monomethylamine 50 50 0 30 100 30 Example 1-9 Monomethylamine 50 50 0 3060 30 Example 1-10 Trimethylamine 75 25 0 30 100 30 Example 1-11Trimethylamine 25 75 0 30 100 30 Comparative Ammonia 50 50 0 30 100 30Example 1-1 Comparative Ammonium 50 0 50 10 100 30 Example 1-2 fluorideComparative Ammonia 50 50 0 30 60 30 Example 1-3 Comparative Not added 050 50 10 100 30 Example 1-4 Comparative Trimethylamine 50 0 50 30 100 30Example 1-5 Comparative Water 10 50 40 30 100 30 Example 1-6 ComparativeMethanol 10 50 40 30 100 30 Example 1-7 Comparative Isopropyl 10 50 4030 100 30 Example 1-8 alcohol

TABLE 1-2 Evaluation result after etching p-Si SiO₂ SiN etching etchingetching SiO₂/SiN amount amount amount selection Presence [nm] [nm] [nm]ratio of residue Example 1-1 <1 98 9 10.9 No Example 1-2 <1 30 2 15.0 NoExample 1-3 <1 96 7 13.7 No Example 1-4 <1 86 7 12.3 No Example 1-5 <138 14 2.7 No Example 1-6 <1 38 10 3.8 No Example 1-7 <1 34 11 3.1 NoExample 1-8 <1 39 6 6.5 No Example 1-9 <1 24 8 3.0 No Example 1-10 <1120 13 9.1 No Example 1-11 <1 83 5 17.1 No Comparative <1 31 17 1.8 YesExample 1-1 Comparative <1 21 16 1.3 Yes Example 1-2 Comparative <1 2219 1.2 Yes Example 1-3 Comparative <1 3 5 0.6 No Example 1-4 Comparative<1 <1 <1 — No Example 1-5 Comparative <1 2 16 0.1 No Example 1-6Comparative <1 5 13 0.4 No Example 1-7 Comparative <1 11 12 0.9 NoExample 1-8

In Examples 1-1 to 1-11, the silicon oxide was etched, and no residueremained on the surface of the thermal oxide film on the wafer B. InComparative Examples 1-1 to 1-3, residues remained. X-ray photoelectronspectroscopy (XPS) of the residues on the surfaces of the thermal oxidefilms in Comparative Examples 1-1 to 1-3 detected ammonium fluoride(NH₄F), ammonium hydrogen fluoride (NH₄F·HF), or ammoniumhexafluorosilicate ((NH₄)₂SiF₆).

Specifically, trimethylamine hydrofluoride (NMe₃·HF) or (HNMe₃)₂SiF₆that was a reaction product of trimethylamine, HF, and silicon oxide inExamples 1-1, 1-2, 1-5, 1-10, or 1-11 had a high vapor pressure and wassufficiently removed even at a temperature of 60° C. or 100° C.Moreover, a reaction product of dimethylamine, HF, and silicon oxide anda reaction product of diethylamine, HF, and silicon oxide had a highervapor pressure than ammonium hexafluorosilicate. Such reaction productsin Examples 1-3, 1-4, 1-5, and 1-6 were also sufficiently removed evenat a temperature of 60° C. or 100° C. In contrast, ammoniumhexafluorosilicate in Comparative Examples 1-1 to 1-3 had a low vaporpressure and was not sufficiently removed at a temperature of 60° C. or100° C. Consequently, residues of ammonium hexafluorosilicate and thelike remained on the surface of the thermal oxide film on the wafer.Meanwhile, if heat treatment at a temperature of higher than 200° C. isconducted after the contact with the treatment gas in ComparativeExamples 1-1 to 1-3, residues remaining on the surface of the thermaloxide film in the wafer can be removed.

In Examples 1-8 and 1-9, the results demonstrate that the silicon oxidewas etched with no residue even when monomethylamine was used.Comparison of the silicon oxide-etching speeds among Examples 1-1, 1-3,1-5, 1-6, 1-8, and 1-9 and Comparative Examples 1-1 and 1-3 at the sametemperature reveals that the speed with monomethylamine which is aprimary amine is higher than the speed with ammonia but is lower thanthe speed with dimethylamine which is a secondary amine or the speedwith trimethylamine which is a tertiary amine.

In Comparative Example 1-4 in which only HF was contacted, the siliconoxide-etching speed was lower, and the silicon oxide/silicon nitrideetching selection ratio (SiO₂/SiN selection ratio) was low. InComparative Example 5 in which only the organic amine compound wascontacted, none of the polycrystalline silicon, the silicon oxide, andthe silicon nitride was etched. In Comparative Examples 1-6, 1-7, and1-8 in which water, methanol, and isopropyl alcohol, respectively, wereused together with HF gas, the SiO₂-etching speed was low, and theSiO₂/SiN selection ratio was low.

Comparisons at the same temperature between Examples 1-1 to 1-4 andComparative Examples 1-1 and 1-2 and between Examples 1-5 to 1-7 andComparative Example 1-3 revealed that the SiO₂-etching speed was higherand the SiO₂/SiN selection ratio was higher in the examples than in thecomparative examples. Moreover, in Examples 1-1 to 1-4, 1-10, and 1-11in which the contact with the treatment gas was conducted at 100° C.,the SiO₂/SiN selection ratio exceeded 8.

Examples 2-1 to 2-3, Comparative Examples 2-1 and 2-2

Etching evaluation was conducted by a method involving supplying anorganic amine compound first and then supplying HF gas.

The wafer A, B, or C was placed on a stage in the chamber. The chamberwas evacuated to 10 Pa or lower, and the temperature of the stage wasadjusted to a predetermined temperature indicated in Table 2. Then, atreatment gas including amine was supplied into the chamber, and thepressure was maintained at 30 Torr (4 kPa) for 30 seconds. The chamberwas evacuated to 0.1 kPa, and a treatment gas including HF gas wassupplied into the chamber. The state at a pressure of 30 Torr (4 kPa)was maintained for 30 seconds. Subsequently, the atmosphere in thechamber was evacuated to 10 Pa or lower and then replaced with an inertgas. Next, the wafer A, B, or C was taken out, and its thickness wasmeasured, thereby evaluating the etching amount. Separately, a surfaceof the thermal oxide film on the silicon wafer B after the etching wasobserved with an optical microscope to examine the presence of residueson the surface.

Table 2 shows the types and temperatures of amines and evaluationresults after etching.

In Comparative Example 2-2, only a treatment gas including HF gas wassupplied without supplying amine.

TABLE 2 Evaluation result after etching Etching conditions p-Si SiO2 SINOrganic amine, Temper- etching etching etching SiO2/SiN etc. atureamount amount amount selection Presence Type [° C.] [nm] [nm] [nm] ratioof residue Example 2-1 Trimethylamine 100 <1 99 9 11.0 No Example 2-2Dimethylamine 100 <1 85 28 3.0 No Example 2-3 Monomethylamine 100 <1 3814 2.7 No Comparative Ammonia 100 <1 32 17 1.9 Yes Example 2-1Comparative Not added 100 <1 3 5 0.6 No Example 2-2

As demonstrated in Examples 2-1 to 2-3, when a treatment gas including ahydrogen fluoride was supplied after supplying a treatment gas includingan organic amine compound, the silicon oxide was etched with no residue.

The silicon oxide-etching speeds in Examples 2-1 to 2-3 were higher thanin Comparative Example 2-1 in which ammonia was used. The siliconoxide-etching speed with dimethylamine which is a secondary amine ortrimethylamine which is a tertiary amine was higher than the speed withmonomethylamine which is a primary amine. In particular, withtrimethylamine which is a tertiary amine, the SiO₂/SiN selection ratioexceeded 10.

REFERENCE SIGNS LIST

-   -   1 reactor (etching apparatus)    -   2 chamber (treatment container)    -   3 stage    -   4 sample (substrate to be treated)    -   5 a hydrogen fluoride gas supplier    -   5 b organic amine compound gas supplier    -   5 c inert gas supplier    -   6 gas emission line    -   7 manometer    -   8 heater

1. A method of dry-etching silicon oxide, comprising reacting siliconoxide with any one of the following (A) to (C): (A) a gaseous hydrogenfluoride and a gaseous organic amine compound, (B) a gaseous hydrogenfluoride salt of an organic amine compound, and (C) a gaseous hydrogenfluoride, a gaseous organic amine compound, and a gaseous hydrogenfluoride salt of an organic amine compound, in a non-plasma state. 2.The dry-etching method according to claim 1, wherein a temperature ofthe silicon oxide upon the reaction is 200° C. or lower.
 3. Thedry-etching method according to claim 1, wherein the reaction comprisescontacting silicon oxide with a treatment gas including any one of thefollowing (a) to (c): (a) a hydrogen fluoride and an organic aminecompound, (b) a hydrogen fluoride salt of an organic amine compound, and(c) a hydrogen fluoride, an organic amine compound, and a hydrogenfluoride salt of an organic amine compound.
 4. The dry-etching methodaccording to claim 1, wherein a ratio of the organic amine compound tothe hydrogen fluoride included in the treatment gas, as determined bydividing the number of moles of the organic amine compound by the numberof moles of the hydrogen fluoride, is 0.001 or higher but 100 or lower.5. The dry-etching method according to claim 1, wherein the reactioncomprises: contacting a treatment gas including an organic aminecompound with silicon oxide; and contacting a treatment gas including ahydrogen fluoride with the silicon oxide.
 6. The dry-etching methodaccording to claim 1, wherein the organic amine compound is representedby the following formula (1):

represents a nitrogen atom, R¹ represents a C1-C10 hydrocarbon groupoptionally having a ring, a heteroatom, or a halogen atom, and R² and R³each represent a hydrogen atom or a C1-C10 hydrocarbon group optionallyhaving a ring, a heteroatom, or a halogen atom, provided that: thehydrocarbon group, when it has a carbon number of three or more,optionally has a branched chain structure or a ring structure; theheteroatom in the hydrocarbon group is a nitrogen atom, an oxygen atom,a sulfur atom, or a phosphorus atom; le and R², when both of them arehydrocarbon groups having a carbon number of one or more, are optionallydirectly bonded to each other to form a ring structure; R¹ and R², whenthey are directly bonded to each other via a double bond to form a ringstructure, they optionally form an aromatic ring in the absence of R³;and R¹, R₂, and R³ are optionally hydrocarbon groups which are the sameas or different from one another.
 7. The dry-etching method according toclaim 1, wherein the organic amine compound is a secondary amine or atertiary amine.
 8. The dry-etching method according to claim 7, whereinthe secondary amine is at least one compound selected from the groupconsisting of dimethylamine, diethylamine, di-normal propylamine,diisopropylamine, dibutylamine, and di-tertiary butylamine.
 9. Thedry-etching method according to claim 7, wherein the tertiary amine isat least one compound selected from the group consisting oftrimethylamine, dimethylethylamine, diethylmethylamine, andtriethylamine.
 10. The dry-etching method according to claim 1, furthercomprising selectively etching a silicon oxide film on a substrate to betreated where both the silicon oxide film and a silicon nitride film areexposed.
 11. The dry-etching method according to claim 10, wherein aselection ratio of the silicon oxide film to the silicon nitride film is2.5 or higher.
 12. A method of producing a semiconductor device,comprising etching a silicon oxide film on a semiconductor substrateincluding the silicon oxide film using the dry-etching method accordingto claim
 1. 13. A dry-etching gas composition comprising any one of thefollowing (a) to (c): (a) a hydrogen fluoride and an organic aminecompound, (b) a hydrogen fluoride salt of an organic amine compound, and(c) a hydrogen fluoride, an organic amine compound, and a hydrogenfluoride salt of an organic amine compound.
 14. The dry-etching gascomposition according to claim 13, wherein the composition substantiallyconsists only of any one of the following (a) to (c): (a) a hydrogenfluoride and an organic amine compound, (b) a hydrogen fluoride salt ofan organic amine compound, and (c) a hydrogen fluoride, an organic aminecompound, and a hydrogen fluoride salt of an organic amine compound. 15.An etching apparatus for etching a silicon oxide film from a substrate,the apparatus comprising: a treatment container provided with a stageconfigured to carry a substrate including a silicon oxide film; ahydrogen fluoride gas supplier configured to supply a treatment gasincluding a hydrogen fluoride into the treatment container; an organicamine compound gas supplier configured to supply a treatment gasincluding an organic amine compound into the treatment container; avacuum evacuator configured to reduce the pressure inside the treatmentcontainer; and a heater configured to heat the stage.
 16. Hydrogenfluoride for use in the dry-etching method according to claim
 1. 17. Anorganic amine compound for use in the dry-etching method according toclaim
 1. 18. The organic amine compound according to claim 17, whereinthe organic amine compound is represented by the following formula (1):

wherein N represents a nitrogen atom, R¹ represents a C1-C10 hydrocarbongroup optionally having a ring, a heteroatom, or a halogen atom, and R²and R³ each represent a hydrogen atom or a C1-C10 hydrocarbon groupoptionally having a ring, a heteroatom, or a halogen atom, providedthat: the hydrocarbon group, when it has a carbon number of three ormore, optionally has a branched chain structure or a ring structure; theheteroatom in the hydrocarbon group is a nitrogen atom, an oxygen atom,a sulfur atom, or a phosphorus atom; R¹ and R², when both of them arehydrocarbon groups having a carbon number of one or more, are optionallydirectly bonded to each other to form a ring structure; R¹ and R², whenthey are directly bonded to each other via a double bond to form a ringstructure, they optionally form an aromatic ring in the absence of R³;and R¹, R², and R³ are optionally hydrocarbon groups which are the sameas or different from one another.
 19. The dry-etching method accordingto claim 2, wherein a temperature of the silicon oxide upon the reactionis 50° C. or higher and 200° C. or lower.
 20. The dry-etching methodaccording to claim 1, wherein when the reaction product of the reactionsublimates into a gas as soon as it is generated, so that the siliconoxide is removed.